Manufacture of nitrogenous compounds derived from perylene quinone



Patented Nov. 21, 1933 7 1,935,721

MANUFACTURE OF NITROGENOUS COM- POUNDS DERIVED FROM PERYLENE- QUINONE Max Albert Kunz, Mannheim, and Karl Koeberle, Ludwigshafen on-the-Rhine, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application November 14, 1929, Serial No. 407,273, and in Germany December 7 Claims. (01. 260-61) The present invention relates to the manu- The compounds which are obtainable in excelfacture of nitrogenous compounds derived from lent yields dissolve in concentrated sulfuric acid perylene quinone. usually to give a red-violet, blue or green colora- We have found that new and valuable comtion and their vat'solutions are usually from pounds containing nitrogen which are in part Violet red to blue in color; cotton is dyed a great suitable as intermediate products for the manuvariety of shades from these vats. The crude facture of dyestuffs and in part as-dyestuffs, are compounds containing nitrogen may be purified, obtainable when perylene quinone, ms-benzdianif desired, by boiling up with organic solvents, or throne, ms-naphthodi-anthrone, allo-ms-naphby treating pastes of the same with oxidizing 1o thodianthrone, ms-anthradianthrone or their agents, for example with alkali metal hypomethyl or halogen derivatives are subjectchlorite, or by dissolving them in concentrated ed to the action of hydroxylamine or its salts, sulfuric acid reprecipitating them from the said preferably in an acid inorganic dissolving solution by the additionof water or dilute sul-- or suspending medium capable of splitting off furic acid. I 15 water, such as for example sulfuric acid, The following examples will further illustrate 7 phosphoric acid, chlorosulfonic acid and the like. the nature of this invention, but the invention 0 Condensing catalysts, forexample metals or is not restricted to these examples. The parts metal compounds, such as iron, copper, mercury are by weight. and the like, or iron or copper sulfate, may be 0 added to the reaction mixture. Example 1 By the process in accordance with the present 58 parts of perylene-3.10-quinone are dissolved invention, the manufacture of the'perylene quiin 1000 parts of concentrated sulfuric acid and nones from intermediate products and the'treatafter the addition of 100 parts of ferrous sulfate ment with hydroxylamine may be advantageously and parts of hydroxylamine sulfate the whole 25 effected in one working operation, whereby in is heated up to from 140 to 150 C., while stirring.

some cases products different from those produced The whole is maintained at the same temperature from the ready-made perylene quinones are obuntil a sample taken out when poured into ice tained. -Thus, for example, when treating water separates out in the form of a flocculent perylene in concentrated sulfuric acid with grey violet precipitate. The reaction mixture is 0 hydroxylamine, a nitrogenous compound of then allowed to cool, is poured onto ice andfiltered perylene quinone is obtained which is different off by suction. The reaction product which confrom that'obtained by the action of hydroxyltains nitrogen dissolves in concentrated sulfuric amine on perylene-3.10-quinone. When treatacid giving a violet coloration, and gives a violet' ing ms-benzdianthrone in concentrated sulfuric vat from which cotton is dyed grey shades which 5 acid with hydroxylamine further condensation become orangeunder the action of hypochlorite to a derivative of ms-naphthodianthrone takes or chlorine. g place bythe addition of oxidizing agents, such as, for example, pyrolusite, or by simply raising the temperature. Likewise when starting from 1.1'- 25.2 parts of perylene are introduced, while stir-i 4 dianthraquinonyl, this may be converted into msring, at ordinary temperature into asuspension of a benzdianthrone by the action of reducing agents 40 parts of hydroxylamine sulfate and parts 95 in sulfuric acid solution, the ms-benzdianthrone of ferrous sulfate in 500 parts of concentrated being converted by the simultaneous or consecusulfuric acid. The temperature is slowly raised tive action of hydroxylamine into a nitrogenous to from to C. and the whole is kept at 45 derivative. this temperature until the color of the reaction Particularly valuable dyestuffs obtainable mass has become pure blue. When cooled, the according to our invention are, due to their good reaction product separates out in the form of aflinity to vegetable fibers, those of the new the oxonium sulfate which is either filtered off nitrogenous compounds as are derived from by suction, decomposed with water and isolated 50 perylene quinones in which two anthracene rings in the usual manner or is poured directly into ice 105 are connected to each other by at least two water and isolated. hexagon rings, that is to say, the nitrogenous The reaction product obtained, which is a black compounds derived from ms-naphthodianthrone, powder is practically insoluble in all organic solallo-ms-naphthodianthrone and ms-anthradianvents and only dissolves with difiiculty in concen- 55I throne. trated sulfuric acid giving a blue coloration in Example 2v contradistinction to the product obtainable according to Example 1 which is more readily soluble in concentrated sulfuric acid. It contains nitrogen and yields a violet vat from which cotton is dyed grey shades.

Example 3 I v 38 parts of ms-benzdianthrone are. dissolved,

' while stirring, in 600 parts of, concentrated sulfuric acid. After the addition of 19 parts of hydroxylamine sulfate and parts of ferrous sulfate the temperature is slowly raised to from 150 to 170 C. and the whole is kept at this ternperature until the solution has become violet red.

. Example 4 203 parts of 2.2"-dimethyl-ms-naphthodianthrone aredissolved, while stirring, in 5000 parts of concentrated sulfuric acid and after the addition of 200 parts of hydroxylamine sulfate. and 500 parts of ferrous sulfate, the whole is slowly heated to from 160 to 170 C. and kept at this temperature until a sample taken out yields a fiocculent brown precipitate upon the addition of water. It is then worked up in the usual manner. The condensation product containing nitrogen thus obtained, which is a brown powder, dissolves in concentrated sulfuric acid giving a violet coloration and constitutes a valuable intermediate product for the manufacture of dyestuffs.

Erample 5 100 parts of alloms-naphthodianthrone are dissolved, while stirring, in 1000 parts of concentrated sulfuric acid. 50 parts of hydroxylamine sulfate and 500 parts of ferrous sulfate are added to this solution at ordinary temperatures and the whole is heated to from 140 to 160? C. When the initial emerald green coloration has changed through a blue to pure violet the reaction product is worked up as described in Example 1. The reaction product containing nitrogen obtained, which is a violet black powder, dissolves in concentrated sulfuric acid giving. aviolet coloration and dyes cotton powerful grey shades from a blue vat.

Example 6 5.4 parts of dibromoperylene-3.lo-quinone (obtainable by brominating perylene-3.10-quinone in aqueous suspension) are dissolved in 54 parts of concentrated sulfuric acid. After the addition of 2 parts of hydroxylamine hydrochloride the temperature of the reaction mixture is raised, while stirring, to 170 C. and kept thereat for several hours, the reaction mixture being then allowed to cool and worked up'in the usual manner. .The reaction product containing bromine and nitrogen thus obtained dissolvesv in concentrated sulfuric acid to give a. blue red solution and dyes none, ms-benzdianthrone, 'ms-naplrthodianthrone, allo-ms-naphthodianthrone, ms-anthradianthrone, which may be substituted by methyl or halogen dissolving in, concentrated sulfuric acid to give from red violetto green solutions and giving from violet to blue vats, the said products being obtainable by heating one of the said compounds with hydroxylamine.

2. Nitrogenous derivatives of dianthrones corresponding to the formula:

0 II o in which the two anthrone nuclei are connected with each other with at least one further hexagon ring, which nitrogenous derivatives dissolve in concentrated sulfuricacid to give from red to violet solutions and dyeing cotton, from blue red to blue green vats brown to grey shades, and are obtainable by heating one of the said dianthrones with hydroxylamine.

3. The process of producing nitrogenous compounds, which comprises heating a compound selected from the group consisting of perylenequinone, ms-benzdianthrone, ms-naphthodianthrone, allo-ms-naphthodianthrone, ms-anthradianthrone, which. may be substitutedby methyl or halogen with hydroxylamine.

4. The process'of producing nitrogenous compounds, which comprises heating a compound selected from the group consisting of perylenequinone, msbenzdianthrone, ms-naphthodianthrone, allo-ms-naphthodianthrone, Ins-anthradianthrone, which may be substituted by methyl or halogenwith hydroxylamine in the presence of, an inorganic acid capable of splitting off water. 4

5. The porcess of producing nitrogenous compounds, which comprises heating a compound selected from the group consisting of perylenequinone, ms-benzdianthrone, ms-naphthodianthrone, allo-ms-naphthodianthrone, ins-anthradianthrone; which may be substituted by methyl or halogen with hydroxylamine in thefpresence of an inorganic acid capable of splitting off water and a condensing catalyst.

6. The process of producing nitrogenous compounds, Which comprises heating a compound selected from the group consisting of perylenequinone, ms-benzdianthrone, ms-naphthodianthrone, allo-ms-naphthodianthrone, ms-anthradianthrone, which may besubstituted by methyl or halogen with hydroxylamine in the presence of concentrated sulfuric acid.

'7. The process of producing an aminoperylene- 3.10-quinone, which comprises heating perylene- 3.l0-quinone with hydroxylamine in the presence of concentrated sulfuric'acid and ferrous sulfate. 1 I

" MAX ALBERT KUNZ.

KARL KOEBERLE. 

